Process for producing modified epoxy resin

ABSTRACT

This invention provides a process for producing an epoxy resin composition having core/shell rubber particles (rubber-like polymer particles) dispersed in an epoxy resin, wherein an epoxy resin composition excellent in the dispersed state of rubber-like polymer particles in an epoxy resin with a reduced amount of contaminants is produced easily and efficiently. 
     The epoxy resin composition having rubber-like polymer particles dispersed well in an epoxy resin with less contaminant is obtained by bringing an aqueous latex of rubber-like polymer particles (B) into contact with an organic medium (C) showing partial solubility in water, then bringing an organic medium (D) having lower partial solubility in water than that of the organic medium (C) into contact therewith to separate water substantially, to remove the rubber-like polymer particles as a dispersion (F) having the polymer particles dispersed in the organic medium, and mixing it with an epoxy resin (A), followed by distilling volatile components away.

RELATED APPLICATION

This application is a national stage of International Application No.PCT/JP2004/007679, filed on May 27, 2004, claiming priorities based onJapanese Application No. 2003-164416 filed on Jun. 9, 2003, the contentsof all of which are incorporated herein by reference in their entirety.

TECHNICAL FIELD

The present invention relates to a process for producing arubber-modified epoxy resin composition.

BACKGROUND ART

A cured product of epoxy resin is superior in many aspects such asdimensional stability, mechanical strength, electrical insulatingproperties, heat resistance, water resistance and chemical resistance.However, the cured product of epoxy resin is poor in fracture toughnessand may show very brittle properties, and such properties are oftenproblematic in various uses.

As a means to solve these problems, incorporation of rubber componentsinto the epoxy resin has been conventionally conducted. In particular, amethod of incorporating rubber-like polymer particles previouslyprepared in the form of particles by using a polymerization method in anaqueous medium, represented by emulsion polymerization, dispersionpolymerization and suspension polymerization, is considered advantageousin principle in that a dispersed state is hardly changed under blendingand curing conditions, a continuous phase of a cured product of epoxyresin is not contaminated with rubber components by previouslycrosslinking the rubber components, so that heat resistance andtoughness are hardly reduced, as compared with a method of forming adispersed phase of rubber components in a continuous phase of a curedproduct of epoxy resin by causing phase separation during a curingprocess after dissolving and mixing non-crosslinked rubber componentswith epoxy resin, and thus the following various production methods havebeen proposed.

-   (1) A method which comprises milling a coagulated material of a    rubber-like polymer latex and then mixing it with an epoxy resin    (for example, Jp-A 5-295237 and Japanese patent No. 2751071).-   (2) A method which comprises mixing a rubber-like polymer latex with    an epoxy resin and then distilling water away to give a mixture    (see, for example, Jp-A 6-107910).-   (3) A method which comprises mixing a rubber-like polymer latex with    an epoxy resin in the presence of an organic solvent to give a    mixture (see, for example, U.S. Pat. No. 4,778,851).

Usually when rubber-like polymer particles obtained as aqueous latex areto be mixed and dispersed in an epoxy resin, the rubber-like polymershould be separated from water.

In the method (1), the rubber-like polymer is separated from water byisolating it once as a coagulated material, but handling of thismaterial and the step of mixing it with an epoxy resin are complicatedand industrially not preferable. When the rubber-like polymer removedonce as a coagulated material is to be mixed and re-dispersed in anepoxy resin, the rubber-like polymer particles are hardly re-dispersedin the form of primary particles in the epoxy resin, even by using amilling or dispersing procedure with significant mechanical shear force.

In the method (2), the epoxy resin is hardly mixed with water so that apart of the resin not mixed with water is dried to form a resin chunk,which unless removed, adversely affects qualities. In addition, a largeamount of water should be removed in the presence of the epoxy resin, tomake the procedure difficult.

In the method (3), while mixing the rubber-like latex with the epoxyresin, a large amount of water (an excess of water which cannot bedissolved in an organic solvent) present in the mixture in the systemtogether with an organic solvent should be separated or distilled away,but the separation of the aqueous layer from the organic solvent layerrequires much time such as whole day, or is substantially difficultbecause the organic solvent layer and the aqueous layer form a stableemulsified or suspended state. When water is to be distilled away, alarge amount of energy is necessary, and water-soluble contaminants suchas an emulsifier, auxiliary materials etc. used usually in production ofthe rubber-like polymer latex remain in the composition to make itinferior in qualities. Accordingly, removal of water by either method ofseparating or distilling water is troublesome and industrially notpreferable.

DISCLOSURE OF THE INVENTION

The object of the present invention is to provide an easy and efficientprocess for producing a rubber-modified epoxy resin composition havingrubber-like polymer particles incorporated into an epoxy resin, whichcomprises separating water efficiently from the rubber-like polymerparticles obtained in the state of an aqueous latex without isolatingthe particles as a coagulated material, and then mixing the rubber-likepolymer particles with an epoxy resin, wherein the rubber-like polymerparticles can be mixed and dispersed uniformly in the epoxy resin, whilecontaminants such as an emulsifier added at the time of polymerizationof the rubber-like polymer particles can be removed simultaneously.

That is, the present invention relates to a process for producing anepoxy resin composition having rubber-like polymer particles (B)dispersed and mixed stably in an epoxy resin (A), whichcomprises-bringing an organic medium (C) showing partial solubility inwater into contact with an aqueous latex of rubber-like polymerparticles (B), then bringing an organic medium (D) having lower partialsolubility in water than that of (C) into contact therewith to separatean aqueous layer substantially from the rubber-like polymer particles(B), mixing the resulting dispersion (F) comprising the rubber-likepolymer particles (B) and the mixed organic mediums (C) and (D), with anepoxy resin (A), and removing volatile components.

In the process of the present invention, it is preferable that beforethe dispersion (F) is mixed with the epoxy resin (A), the dispersion (F)is washed by bringing it at least once into contact with water, and itis more preferable also that after the organic medium (C) showingpartial solubility in water is brought into contact with the aqueouslatex of rubber-like polymer particles (B) and before the organic medium(D) is brought into contact therewith, the dispersion is brought intocontact with water at least once.

It is also preferable that the solubility of water in the organic medium(C) showing partial solubility in water is preferably 9 to 40% byweight, and also that the organic mediums (C) and (D) are a combinationnot forming two-component azeotropic mixture.

It is preferable that the rubber-like polymer particles (B) in theprocess of the invention are obtained by graft-polymerizing 5 to 50% byweight of a shell layer (B-2) comprising at least one monomer selectedfrom the group consisting of (meth)acrylates, aromatic vinyls, vinylcyanides, unsaturated acid derivatives, (meth) acrylamide derivativesand maleimide derivatives, with 50 to 95% by weight of a rubber particlecore (B-1) comprising elastic materials composed of not less than 50% byweight of at least one monomer selected from the group consisting ofdiene monomers and (meth)acrylate monomers and less than 50% by weightof another copolymerizable vinyl monomer, or polysiloxane rubber elasticmaterials, or a mixture thereof, and it is more preferable that theshell layer (B-2) in the rubber-like polymer particle (B) comprises as aconstitutional element a monomer having reactivity with an epoxy resinor a curing agent at the time of curing reaction of the epoxy resin.

Further, the present invention relates to a dispersion (F) comprisingrubber-like polymer particles (B) and organic mediums (C) and (D), whichis obtained by bringing an organic medium (C) showing partial solubilityin water into contact with an aqueous latex of rubber-like polymerparticles (B) and then bringing an organic medium (D) having lowerpartial solubility in water than that of (C) into contact therewith toseparate an aqueous layer substantially from the rubber-like polymerparticles (B).

In addition, the present invention relates to an epoxy resin compositionobtained by the above-described process for producing an epoxy resincomposition and also to a cured molded product comprising the epoxyresin composition cured with a curing agent.

The present invention relates to a production process wherein an epoxyresin composition comprising the rubber-like polymer particles (B)dispersed stably in the epoxy resin (A) is obtained. The presentinvention relates in particular to a production process wherein therubber-like polymer (B) obtained in the state of an aqueous latex iseasily and efficiently mixed and dispersed in the epoxy resin (A). Theepoxy resin composition obtained by the present invention is an epoxycomposition comprising the rubber-like polymer particles (B) welldispersed in the epoxy group-containing liquid resin (A).

The epoxy resin (A used in the present invention is a prepolymer havingan epoxy group. The epoxy resin which can be used in the presentinvention is an epoxy resin also called polyepoxide. An example thereofis a bisphenol A diglycidyl ether, novolak epoxy resin, tri- ortetrafunctional epoxy resin, polymerized epoxy resin (for example,diglycidyl ether of polymerized bisphenol A) or homopolymer or copolymerobtained by polymerizing unsaturated monoepoxide (for example, glycidyl(meth)acrylate, allyl glycidyl ether).

The polyepoxide used in the present invention includes glycidyl ether ofpolyvalent alcohol and polyvalent phenol, polyglycidyl amine,polyglycidyl amide, polyglycidyl imide, polyglycidyl hydantoin,polyglycidyl thioether, epoxidated fatty acid or epoxidated dry oil,epoxidated polyolefin, epoxidated unsaturated polyester, and a mixturethereof. Many polyepoxides synthesized from polyvalent phenol aredisclosed in for example U.S. Pat. No. 4,431,782. The polyepoxide issynthesized from monovalent, divalent or trivalent phenol, and alsoincludes novolak resin. The polyepoxide also includes polyepoxidesconsisting of a polymer or copolymer of glycidyl (meth)acrylate or allylglycidyl ether in addition to epoxidated cycloolefin. Preferableexamples of the polyepoxide include those described in U.S. Pat. Nos.3,804,735, 3,892,819, 3,948,698, and 4,014,771 and “Epoxy ResinHandbook” (The Nikkan Kogyo Shimbun Ltd., 1987).

The poly epoxide used in the present invention is as described above,and includes polyepoxides generally having an epoxy equivalent weight of80 to 2000. These polyepoxides can be obtained by a known method,generally by a method of reacting an excess of epihalohydrin with apolyvalent alcohol or polyvalent phenol.

The polyepoxide used in the present invention may contain a monoepoxide,for example aliphatic or aromatic glycidyl ether such as butyl glycidylether, phenyl glycidyl ether or glycidyl glycidyl ether as a reactivediluent. As is generally known, the monoepoxide affects thestoichiometry of a polyepoxide composition, which can be adjusted by theamount of a curing agent or by other known methods.

The epoxy resin (A) used in the present invention can also contain acuring agent and/or a curing accelerator for the epoxy group-containingcompound, but such additives are desired not to substantially cause anunintended curing reaction with the epoxy resin under the productionconditions in the present invention. As the curing agent and/or curingaccelerator, only those described in the above-mentioned Epoxy ResinHandbook and satisfying the requirements of the present invention can beused.

In the process for producing the epoxy resin composition according tothe present invention, the rubber-like polymer particles (B) arepreferably made of a core/shell polymer composed of the rubber particlecore (B-1) comprising a polymer based on an elastomer or a rubber-likepolymer and the shell layer (B-2) comprising a polymer componentgraft-polymerized therewith.

The polymer constituting the rubber particle core (B-1) is cross linked,and the polymer constituting the rubber-like core (B-1) can be swollenwith, but is not substantially dissolved in, a suitable solvent. Therubber particle core (B-1) is insoluble in the epoxy resin (A). Thecontent of gel in the rubber particle core (B-1) is not less than 60% byweight, preferably not less than 80% by weight, still more preferablynot less than 90% by weight, further still more preferably not less than95% by weight. The glass transition temperature (Tg) of the polymerconstituting the rubber particle core (B-1) is 0° C. or less, preferably−100° C. or less.

The polymer constituting the rubber particle core (B-1) preferablycomprises elastic materials composed of not less than 50% by weight ofat least one monomer selected from the group consisting of a dienemonomer (conjugated diene monomer) and a (meth) acrylate monomer andless than 50% by weight of another copolymerizable vinyl monomer, orpolysiloxane rubber elastic materials, or a mixture thereof. In thepresent invention, (meth)acryl means acryl and/or methacryl.

The conjugated diene monomer constituting the elastic materialsincludes, for example, butadiene, isoprene, chloroprene etc., amongwhich butadiene is particularly preferable. The (meth)acrylate monomerincludes, for example, butyl acrylate, 2-ethylhexyl acrylate, laurylmethacrylate etc., among which butyl acrylate and 2-ethylhexyl acrylateare particularly preferable. These can be used alone or as a mixture oftwo or more thereof.

The amount of at least one kind of monomer selected from the groupconsisting of a conjugated diene monomer and a (meth)acrylate monomer ispreferably not less than 50% by weight, more preferably not less than60% by weight, based on the total weight of the elastic materials. Whenthe amount of the monomer used is less than 50% by weight, the rigidityimprovement effect of the epoxy resin composition of the presentinvention tends to be lowered.

Further, the elastic materials may be composed not only of theconjugated diene monomer or (meth) acrylate monomer but also of acopolymer thereof with a vinyl monomer copolymerizable therewith. Thevinyl monomer copolymerizable with the conjugated diene monomer or(meth)acrylate monomer includes monomers selected from the groupconsisting of an aromatic vinyl monomer and a vinyl cyanide monomer. Thearomatic vinyl monomer includes, for example, styrene, α-methylstyreneand vinyl naphthalene, and the vinyl-cyanide monomer includes, forexample, (meth)acrylonitrile and substituted acrylonitrile. These can beused alone or in combination thereof.

The amount of these copolymerizable vinyl monomers used is preferablyless than 50% by weight, more preferably less than 40% by weight, basedon the total weight of the elastic materials.

To adjust the degree of crosslinkage, a multifunctional monomer may becontained as a component constituting the elastic materials. Examples ofthe multifunctional monomer include divinyl benzene, butane dioldi(meth)acrylate, triallyl (iso)cyanurate, allyl (meth)acrylate, diallylitaconate, diallyl phthalate etc. The amount of the multifunctionalmonomer used is not higher than 10% by weight, preferably not higherthan 5% by weight, more preferably not higher than 3% by weight, basedon the total weight of the elastic materials. When the amount of themultifunctional monomer used is higher than 10% by weight, the rigidityimprovement effect of the epoxy resin composition of the presentinvention tends to be lowered.

To adjust the molecular weight or crosslinking degree of the polymersconstituting the elastic materials, a chain transfer agent may be used,and for example C5 to C20 alkyl mercaptan can be mentioned. The amountof the chain transfer agent used is not higher than 5% by weight, morepreferably not higher than 3% by weight, based on the total weight ofthe rubber particle core (B-1). It is not preferable that the amount ofthe chain transfer agent used is higher than 5% by weight, because theamount of non-crosslinked components in the rubber particle core (B-1)is increased, which may adversely affect the heat resistance, rigidityetc. of a cured epoxy resin product obtained by using the epoxy resincomposition of the present invention.

As the rubber particle core (B-1), polysiloxane rubber type elasticmaterials can be substituted for, or used in combination with, theelastic materials. When the polysiloxane rubber type elastic materialsare used as the rubber particle core (B-1), polysiloxane rubber composedof di-alkyl or aryl substituted silyloxy units such as dimethylsilyloxy, methylphenyl silyloxy and diphenyl silyloxy can be used. Whenthe polysiloxane rubber-mentioned above is used, it is preferable tointroduce previously a cross linked structure into it by using amultifunctional alkoxy silane compound partially in combinationtherewith during polymerization or by radically reacting a silanecompound having a vinyl reactive group introduced in it or using othermethods, if necessary.

The shell layer (B-2) gives affinity for epoxy resin so that therubber-like polymer particles (B) can be dispersed stably in the form ofprimary particles in the epoxy resin.

The polymer constituting the shell layer (B-2) has beengraft-polymerized with the polymer constituting the rubber particle core(B-1) and substantially bonded to the polymer constituting the rubberparticle core (B-1). It is desired that preferably not less than 70% byweight, more preferably not less than 80% by weight and still morepreferably not less than 90% by weight of the polymer constituting theshell layer (B-2) is bonded to the rubber particle core (B-1).

The shell layer (B-2) is preferably having the swellability ormiscibility or affinity to the organic medium (C) and epoxy resin (A)described later. Depending on necessity in use, the shell layer (B-2)may contain monomers reactive with the epoxy resin (A) or with a curingagent incorporated for use. A functional group of the reactive monomercontained in the shell layer (B-2) is preferably the one capable ofchemically reacting with the epoxy resin (A) or the curing agent to forma linkage under conditions where the epoxy resin (A) is cured byreaction with the curing agent.

From the viewpoint of availability and affinity for the organic solvent(C), the polymer constituting the shell layer (B-2) is preferably apolymer or copolymer obtained by copolymerizing at least one componentselected from alkyl(meth)acrylate, an aromatic vinyl compound and avinyl cyanide compound. Particularly when the shell layer (B-2) isdesired to be chemically reactive at the time of curing the epoxy resin,it is preferable from the viewpoint of high reactivity with the epoxygroup or the epoxy curing agent that the polymer constituting the shelllayer (B-2) is made of at least one kind of monomer selected from thegroup consisting of (meth)acrylates having a reactive side chain, suchas hydroxyalkyl (meth)acrylate, aminoalkyl (meth)acrylate and epoxyalkyl(meth)acrylate, epoxy alkyl vinyl ethers, unsaturated acid derivatives,(meth)acrylamide derivatives and maleimide derivatives, in addition tothe alkyl (meth)acrylate, aromatic vinyl compound or vinyl cyanidecompound.

The alkyl (meth)acrylate includes, for example, methyl (meth)acrylate,ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate,etc. The aromatic vinyl includes styrene, α-methylstyrene etc. The vinylcyanide includes (meth)acrylonitrile etc.

The (meth)acrylate having a reactive side chain includes, for example,2-hydroxyethyl (meth)acrylate, 2-aminoethyl (meth)acrylate and glycidyl(meth)acrylate. The epoxy alkyl vinyl ether includes glycidyl vinylether. The unsaturated acid derivative includes α, β-unsaturated acids,α, β-unsaturated acid anhydrides, (meth)acrylic acid, itaconic acid andcrotonic acid. The (meth)acrylamide derivative includes (meth)acrylamide(including N-substituted derivatives thereof). The maleimide derivativeincludes maleic anhydride and maleic imide. These can be used alone orin combination thereof.

The ratio (by weight) of the rubber particle core (B-1)/shell layer(B-2) in the rubber-like polymer particle (B) is in the range ofpreferably 50/50 to 95/5, more preferably 60/40 to 90/10. When the(B-1)/(B-2) ratio is outside of 50/50 to decrease the ratio of therubber particle core (B-1), the rigidity improvement effect of the epoxyresin composition of the present invention tends to be decreased. Whenthe ratio is outside of 95/5 to decrease the ratio of the shell layer(B-2), flocculation easily occurs at the time of handling in the processof the present invention causing a problem in operability and thusdesired physical properties may not be obtained.

The rubber-like polymer particles (B) can be produced by a method knownin the art, such as emulsion polymerization, suspension polymerization,micro-suspension polymerization etc. In particular, a process byemulsion polymerization is preferable.

An emulsifier or dispersion used in the aqueous medium is preferably theone whose emulsion stability is not deteriorated even if the aqueouslatex is neutral. Concrete examples include alkali metal salts orammonium salts of various acids such as alkyl or aryl sulfonic acidrepresented by dioctylsulfosuccinic acid and dodecylbenzenesulfonicacid, alkyl or aryl ether sulfonic acid, alkyl or aryl sulfuric acidrepresented by dodecylsulfuric acid, alkyl or aryl ether sulfuric acid,alkyl or aryl substituted phosphoric acid, alkyl or aryl ethersubstituted phosphoric acid, N-alkyl or aryl sarcosine acid representedby dodecyl sarcosine acid, alkyl or aryl carboxylic acid represented byoleic acid and stearic acid, and alkyl or aryl ether carboxylic acids,nonionic emulsifiers or dispersion such as alkyl or aryl substitutedpolyethylene glycols, and dispersion such as polyvinyl alcohols, alkylsubstituted cellulose, polyvinyl pyrrolidone, and polyacrylic acidderivatives. These can be used alone or as a mixture of two or morethereof.

According to a preferable embodiment of the present invention, theemulsifier or dispersant is used more preferably in the minimum amountin such a range that dispersion stability is not hindered in the processof producing the rubber-like polymer particles (B) latex. In theproduction process of the present invention, more preferably, theemulsifier or dispersant has properties that the emulsifier ordispersant is extracted and washed with an aqueous layer to such anextent that the residual amount does not influence the physicalproperties of the epoxy resin composition to be produced.

In the process for producing the epoxy resin composition of the presentinvention, the diameter of the rubber-like polymer particles (B) is notparticularly limited insofar as the rubber-like polymer particles (B)can be stably obtained in the form of an aqueous latex, but from theviewpoint of industrial productivity, the average particle diameter ispreferably about 0.03 to 2 μm, more preferably about 0.05 to 1 μm, foreasier production.

In the process for producing the epoxy resin composition according tothe present invention, the content of the rubber-like polymer particles(B) is not particularly limited. The resulting epoxy resin compositioncan also be used as a master batch which is used after being dilutedwith an epoxy resin so as to attain a desired amount of the rubber-likepolymer particles (B). The epoxy resin used in dilution may be the samekinds as, or different if necessary from, the epoxy resin (A) in thecomposition. Assuming that the total amount of the epoxy resin (A) andrubber-like polymer particles (B) in the epoxy resin composition is 100%by weight, the content of the rubber-like polymer particles (B) is forexample 0.5 to 80% by weight, preferably 1 to 70% by weight, morepreferably 3 to 60% by weight, still more preferably 3 to 50% by weight.When the amount of the rubber-like polymer particles (B) is less than0.5% by weight, the rigidity improvement effect of the epoxy resincomposition of the present invention tends to be lowered, while when theamount is higher than 80% by weight, the viscosity of the epoxy resincomposition tends to be significantly increased to hinder the operationin the process.

The organic medium (C) showing partial solubility in water, used in thepresent invention, should be an organic medium achieving mixing withoutcoagulating and precipitating the rubber-like polymer particles (B),when an aqueous latex of the rubber-like polymer particles (B) isbrought into contact with the organic medium (C).

The organic medium (C) showing partial solubility in water, used in thepresent invention, is at least one kind of organic solvent or a mixturethereof, preferably an organic solvent or an organic solvent mixture inwhich the solubility of water in the organic solvent (C) at 25° C. is 9to 40% by weight, preferably 10 to 30% by weight. When the solubility ofwater in the organic solvent (C) is higher than 40% by weight, therubber-like polymer particles (B) easily coagulate to hinder theprocedure upon mixing the organic medium (C) with the aqueous latex ofthe rubber-like polymer particles (B), and the amount of water in themixture (F) as the organic layer tends to be increased. When thesolubility of water is less than 9% by weight, a larger amount of therubber-like polymer particles (B) tends to remain in the aqueous layereven after the organic medium (D) is mixed therewith.

The organic medium (C) is preferably at least one kind of organicsolvent satisfying water solubility in the above range, selected fromesters such as methyl acetate, ethyl acetate, propyl acetate and butylacetate, ketones such as acetone, methyl ethyl ketone, diethyl ketoneand methyl isobutyl ketone, alcohols such as ethanol, (iso) propanol andbutanol, ethers such as tetrahydrofuran, tetrahydropyran, dioxane anddiethyl ether, aromatic hydrocarbons such as benzene, toluene andxylene, and halogenated hydrocarbons such as methylene chloride andchloroform, or a mixture thereof. Especially, an organic solvent mixturecontaining methyl ethyl ketone in an amount of preferably at least 50%by weight, more preferably at least 75% by weight is particularlypreferable.

The amount of the organic medium (C) can be varied depending on the typeof the rubber-like polymer particles (B) and the amount of therubber-like polymer particles (B) in the aqueous latex of (B), but ispreferably 50 to 350 parts by weight, more preferably 70 to 250 parts byweight, still more preferably 50 to 200 parts by weight, relative to 100parts by weight of the latex of the rubber-like polymer particles (B).When the amount of the organic medium (C) is less than 50 parts byweight, the amount of the organic medium (C) forming the organic mediumlayer tends to be decreased depending on the type of the organic medium(C), thus making handling of the organic medium layer difficult. Whenthe amount is higher than 350 parts by weight, the amount of the organicsolvent (C) removed is increased thus lowering production efficiency.

The organic solvent (D) having lower partial water solubility than thatof (C) is preferably an organic solvent, or a mixture of two or moreorganic solvents, wherein the solubility of water in the organic solvent(D) at 25° C. is not higher than 8% by weight, preferably not higherthan 6% by weight, more preferably not higher than 4% by weight. Whenthe solubility of water in the organic medium (D) is higher than 9% byweight, the effect of promoting separation of the organic layer from theaqueous layer may be insufficient.

The organic medium (D) is preferably at least one kind of organicsolvent satisfying water solubility in the above range, selected fromesters such as ethyl acetate, propyl acetate and butyl acetate, ketonessuch as diethyl ketone and methyl isobutyl ketone, ethers such asdiethyl ether and butyl ether, aromatic hydrocarbons such as benzene,toluene and xylene, aliphatic hydrocarbons such as hexane, andhalogenated hydrocarbons such as methylene chloride and chloroform, or amixture thereof.

The organic medium (D) can be used in such an amount as to be effectivein promoting the separation of the organic medium layer from the aqueouslayer. Assuming that the amount of the organic medium (C) is 100 partsby weight, the amount of the organic medium (D) is preferably 20 to 1000parts by weight, more preferably 50 to 400 parts by weight, still morepreferably 50 to 200 parts by weight. When the amount of the organicmedium (D) is less than 20 parts by weight, the effect of promoting theseparation of the organic layer from the aqueous layer tends to beinsufficient, while when the amount is higher than 1000 parts by weight,the amount of the organic medium removed tends to be increased thuslowering production efficiency.

The combination of the organic medium (C) and the organic medium (D) ispreferably a combination of (C) and (D) satisfying the aboverequirements and not forming two-component azeotropic mixture, from theviewpoint of facilitating the recovery, separation and re-use of theorganic medium in industrial production. Such combination includes, forexample, a combination of methyl ethyl ketone and methyl isobutylketone, but the present invention is not limited thereto.

In the process for producing the epoxy resin composition in the presentinvention, the rubber-like polymer particles (B) obtained in the form ofan aqueous latex are separated efficiently from water without isolatingas a coagulated material, and then mixed with the epoxy resin (A).Specifically, from the state of the aqueous latex having the rubber-likepolymer particles (B) dispersed in the aqueous layer, the rubber-likepolymer particles (B) are extracted once as the dispersion (F) havingthe rubber-like polymer particles (B) dispersed stably in a layer madeof two kinds of organic mediums (C) and (D) (referred to hereinafter asthe mixed organic medium layer) and then mixed with the epoxy resin (A).

In other words, two kinds of organic mediums (C) and (D) which aredifferent ion partial water solubility satisfying the requirements ofthe present invention are successively brought into contact with theaqueous latex of the rubber-like polymer particles (B) according to theprocess of the present invention, thereby separating the mixture in ashort time into two layers comprising a layer of the organic mediums (C)and (D) (mixed organic medium layer) and a layer mainly based on water(referred to hereinafter as the aqueous layer). The rubber-like polymerparticles (B) can thereby be removed as dispersion (F) having (B)dispersed stably in the mixed organic medium layer made of the organicmediums (C) and (D).

In the present invention, the aqueous latex of the rubber-like polymerparticles (B) is first brought into contact with the organic medium (C)showing partial water solubility, to form a mixture (referred tohereinafter as mixture (E)) having the rubber-like polymer particles (B)extracted from the latex-derived aqueous layer to the layer based on theorganic medium (C). In this step, water derived from the aqueous latexof the rubber-like polymer particles (B) forms an aqueous layer in themixture (E), and a part of this aqueous layer, or substantially a largepart thereof depending on the case, is emulsified, dispersed and mixedin the layer based on the organic medium (C) containing the extractedrubber-like polymer particles (B) so that the mixed water is hardlyseparated even if the mixture is left for a long time.

Then, the organic medium (D) having lower partial water solubility thanthat of the organic medium (C), in other words, more hydrophobic, isbrought into contact with the mixture (E) thus obtained, whereby thewater emulsified, dispersed and mixed in the layer based on the organicmedium (C) can be separated. By contacting with the highlyhydrophobic-organic medium (D), the hydrophobicity of the mixed organicmedium layer formed by mixing the organic mediums (C) and (D) isincreased, and in a layer based on the organic medium (C) in the mixture(E), a large amount of emulsified and dispersed water derived from thelatex of rubber-like polymer particles (B) is excluded (from organiclayer) to the aqueous layer, and prevented from a part of the aqueouslayer being re-emulsified, dispersed or mixed in the mixed organicmedium layer, or the mixed organic medium layer is prevented from beingemulsified and dispersed in the aqueous layer.

The mixed organic medium layer thus obtained, namely, the dispersion (F)comprising the rubber-like polymer particles (B) and a mixed organicmedium of the organic mediums (C) and (D), occurs in such a state thatthe rubber-like polymer (B) is dispersed stably in the mixed organicmedium of the organic mediums (C) and (D). In a preferable embodiment ofthe present invention, the rubber-like polymer particles (B) aredispersed as substantially primary particles in the dispersion (F).

The amount of the rubber-like polymer particles (B′) contained in theaqueous layer separated by this procedure is preferably not higher than5% by weight, more preferably not higher than 3% by weight, based on thetotal amount of the rubber-like polymer particles (B), and mostpreferably the rubber-like polymer particles (B′) are substantially notcontained.

When the more hydrophobic organic medium (D) (than organic medium (C))is brought into contact with the aqueous latex of the rubber-likepolymer particles (B) before the organic medium (C) showing partialwater solubility is brought into contact with the aqueous latex, themixture (E) having the rubber-like polymer particles (B) extracted inthe organic medium based on the organic medium (D) cannot be obtained.

The contact in the above procedure includes not only contact in theinterface between the aqueous latex of the rubber-like polymer particles(B), the organic medium (C) or the mixture (E) and the organic medium(D), but also mixing of the two under gentle stirring conditions, and aspecial device or method is not required, and a device or methodattaining suitable mixing conditions may be used.

Subsequently, the dispersion (F) obtained through these procedures ismixed with the epoxy resin (A). This mixing can be easily achieved by aknown method without using a special equipment or method. The mixing canbe carried out for example by a method or under conditions used indissolving an epoxy resin in an organic solvent. In a series of theseprocedures, the rubber-like polymer particles (B) do not causeirreversible agglomeration, and before and after mixing with the epoxyresin (A), the rubber-like polymer particles (B) maintain an finelydispersed state. In a preferable embodiment of the present invention,the rubber-like polymer particles (B) maintain an independentlydispersed state of substantially primary particles before and aftermixing with the epoxy resin (A).

Further, volatile components based on the organic mediums (C) and (D)are removed from the mixture of the dispersion (F) and epoxy resin (A),whereby the desired epoxy resin composition maintaining a finedispersion of the rubber-like polymer particles (B) in the epoxy resin(A) can be obtained. As the method of removing volatile components,methods known in the arts are applicable. For example, the methodincludes, but is not limited to, a batch method wherein the mixture isintroduced into a vessel and heated at normal pressure or under reducedpressure to distill volatile components away, a method wherein a dry gasis brought into contact with the mixture, a continuous method of usingan evaporator of thin film type, and a method of using an extruderequipped with a volatilization device or a continuous stirring vessel.The conditions such as temperature and necessary time for removingvolatile components can be suitably selected in such a range that theepoxy resin (A) is not reacted and qualities are not deteriorated.

Depending on end use, the epoxy resin composition obtainable in thepresent invention can be used without removing the organic mediums (C)and (D), and also in this case, the rubber-like polymer particles (B)can be dispersed without agglomeration in a solution of the epoxy resin(A) in the mixed organic medium of the remaining organic mediums (C) and(D). The amount of the remaining organic mediums (C) and (D) in theepoxy resin composition can be selected in a proper range, depending onthe use of the epoxy resin composition.

Another aspect of the present invention is that contaminants such as anemulsifier used generally in production of the rubber-like polymerparticle (B) latex and capable of exerting a harmful influence on theepoxy resin (A) can be easily removed. In a more preferable embodimentof the present invention, the contaminants can be reduced or removed byextracting the contaminants from the resulting dispersion (F) into theaqueous layer by washing with water at least once prior to mixing thedispersion (F) with the epoxy resin (A). When higher degree of removalof the contaminants is necessary, the mixture (E) can be washed withwater at least once after the mixture (E) is obtained by contacting andmixing the rubber-like polymer particles (B) with the organic medium (C)and before the organic medium (D) is contacted and mixed with themixture (E).

The temperature at which the organic medium (C) is mixed with therubber-like polymer particles (B) should be adjusted in such a rangethat the effect of the present invention is not deteriorated, becausethe partial solubility can be changed depending on the type of theorganic solvent (C) to change the partial solubility in water. Byutilizing such aspect, the temperature can be suitably adjusted toseparate the organic layer from the aqueous layer in a preferable state.

In the present invention as described above, when the rubber-likepolymer particles (B) are to be mixed and dispersed in the epoxy resin(A), the rubber-like polymer particles (B) are extracted efficiently asdispersion (F) containing the polymer particles dispersed stably in theorganic medium, without isolating the rubber-like polymer particles (B)as a coagulated material, whereby the rubber-like polymer particles (B)can be dispersed in the epoxy resin (A) while maintaining a finedispersion thereof without requiring strong mechanical stirring etc.Further, the amount of water to be separated from the mixture of theepoxy resin (A) and rubber-like polymer particles (B) can be suppressedsignificantly as compared with a conventional method, thus bringingabout an industrial advantage in production efficiency. In theprocedure, it is not necessary to add water-soluble electrolytes whichcan be contaminants, and an emulsifier added to the rubber-like polymerparticles (B), and contaminants such as ionic compounds andwater-soluble compounds can be easily reduced or removed.

The epoxy resin composition produced by the method of the presentinvention described above can be applied in various uses where epoxyresin is usually used, for example in paints, coating agents, fiber orfiller-reinforced composite materials such as aircraft parts, sportinggoods, or structural materials, adhesives, binding agents, andelectronic materials such as semiconductor sealant or electronic circuitsubstrate, by substituting the composition of the present invention fora part or the whole of the epoxy resin, to give a cured product withexcellent in stability of the dispersed state of the rubber-like polymerparticles (B) and less contaminant in the epoxy resin composition or inthe cured product.

EXAMPLES

The present invention is described in detail by reference to theExamples, but the present invention is not limited thereto. Unlessotherwise specified, the terms “parts” and “%” in the Examples andComparative Examples refer to “parts by weight” and “% by weight”,respectively.

The meanings of abbreviations are as follows:

MEK: methyl ethyl ketone

MIBK: methyl isobutyl ketone

First, the analytical measurement methods described in the Examples aredescribed below.

[1] Quantification of the Rubber-like Polymer Particle (B) ComponentContained in the Aqueous Layer

A part of the aqueous layer discharged by a method described in theExamples and Comparative Examples was taken and dried sufficiently at120° C., and the amount of methanol-insoluble components in theresulting residues was determined as the amount of the rubber-likepolymer particle (B) component contained in the aqueous layer.

[2] Dispersed State of the Rubber-Like Polymer Particles (B) in theEpoxy Resin (a)

The epoxy resin composition obtained in each of the Examples andComparative Examples was cured, and the cured product was observed undera transmission electron microscope (TEM) by an ultra-thin section methodto judge the dispersed state of the rubber-like polymer particles (B).

[2-1] Curing of the Epoxy Resin Composition

25 g of epoxy resin composition obtained in each of the Examples andComparative Examples was mixed with 75 g of the same epoxy resin(Epicote 821) and then mixed under stirring with 6 g of piperidine(manufactured by Tokyo Kasei Kogyo Co., Ltd.) as a curing agent. Thismixture was left in a vacuum drying oven and defoamed first under anitrogen atmosphere and then under reduced pressure at 60° C. for 10minutes. Thereafter, this mixture was poured into a mold of 100×150×3 mmin dimensions and maintained at 120° C. for 16 hours to give a curedproduct.

[2-2] Observation of the Dispersed State of the Rubber-like PolymerParticles (B) Under a Transmission Electron Microscopy

A part of the resulting molded product was cut off, and after therubber-like polymer particles (B) were stained with osmium oxide, a thinsection was cut therefrom and observed at 40,000× magnification under atransmission electron microscope (JEM-1200EX manufactured by JEOL,Ltd.), and the dispersed state of the rubber-like polymer particles (B)in the epoxy resin cured product was evaluated by using as an indicatorof particle dispersion ratio (%) calculated by the following method.

Good: particle dispersion ratio was 90% or more.

Not good: particle dispersion ratio was less than 90%.

[2-3] Calculation of the Particle Dispersion Ratio

In the obtained TEM photograph, four squares of 5 cm in side wereselected at random, and the total number B₀, of rubber-like polymerparticles (B) and the number B₁ of rubber-like polymer particles (B) inthe form where three or more polymer particles were contacted with oneanother (when a certain rubber-like polymer particle (B) is contactedwith “n” polymer particles, the number of polymer particles contactedwith one another was regarded as “n”) were determined, and the particledispersion ratio was calculated according to the following equation:Particle dispersion ratio(%)=(1−(B ₁ /B ₀))×100[3] Amount of the Remaining Emulsifier

The amount of the remaining emulsifier was determined by measuring theamount of the emulsifier remaining in the dispersion (F) before mixingwith the epoxy resin (A) and then expressing the amount as a ratio (% byweight) relative to the amount (=100% by weight) of the emulsifier usedin polymerization of the rubber-like polymer particles (B).

[3-1] Sample Pretreatment

In a method described in the Examples, 5 ml dispersion (F) before mixingwith the epoxy resin (A) was collected, evaporated into dryness,introduced together with 50 ml ethanol into a beaker, and stirred for 10minutes, and the supernatant was used as a sample to be analyzed by amethylene blue method.

[3-2] Methylene Blue Method

30 ml water, 10 ml alkaline sodium borate solution and 5 ml methyleneblue solution (0.025% aqueous solution) were introduced into aseparatory funnel. 20 ml chloroform was added thereto and shaken for 3to 5 minutes, to separate and remove a chloroform layer. The aboveprocedure of adding and removing chloroform was repeated untilcoloration of the chloroform layer disappeared. Then, 3 ml dilutesulfuric acid (2.9% aqueous solution), 20 ml chloroform and 2 ml of thesample prepared in (1) were added thereto and shaken for 3 to 5 minutes,and the chloroform layer was measured for its absorption at 650 nm witha spectrophotometer (spectrophotometer UV-2200 manufactured by ShimadzuCorporation) to determine the amount of the emulsifier remaining in thedispersion (F) before mixing with the epoxy resin (A). Thealkaline-sodium borate solution was prepared by mixing 500 ml of 0.4%sodium hydroxide with 500 ml of 1.9% aqueous sodium tetraborate·10H₂O.

[4] Epoxy Equivalent Value (EEW)

The epoxy equivalent value (EEW) of the epoxy resin composition obtainedin a method described in the Examples was measured according to JISK-7236.

Hereinafter, examples of the process for producing the reinforced epoxyresin composition of the present invention are described.

Production Example 1 Production of Rubber-like Polymer Particles (B)

200 parts of water, 0.03 part of tripotassium phosphate, 0.25 part ofpotassium dihydrogen phosphate, 0.002 part of ethylenediaminetetraaceticacid, 0.001 part of ferrous sulfate and 1.5 parts of sodiumdodecylbenzenesulfonate were introduced into a 100 L pressure-resistantpolymerization vessel and purged sufficiently with nitrogen understirring to remove oxygen, and then 75 parts of butadiene and 25 partsof styrene were introduced into the system and heated to 45° C.polymerization was initiated by introducing 0.015 part of p-menthanehydroperoxide and then 0.04 part of sodium formaldehyde sulfoxylate.Four hours after the polymerization was initiated, 0.01 part ofp-menthane hydroperoxide, 0.0015 part of ethylenediaminetetraacetic acidand 0.001 part of ferrous sulfate were introduced. Ten hours afterinitiation of the polymerization, the remaining monomer was removed byvolatilization under reduced pressure to terminate the polymerization.The polymerization conversion ratio was 98%, and the average particlediameter of the resulting styrene-butadiene rubber latex was 0.1 μm.

1300 g of the above rubber latex (containing 420 g of styrene-butadienerubber particles and containing an emulsifier sodiumdodecylbenzenesulfonate in an amount of 1.5% by weight relative to thesolids content of the rubber) and 440 g of pure water were introducedinto the system, and the mixture was purged with nitrogen and stirred at70° C. After 1.2 g of azobisisobutyronitrile (AIBN) was added, a mixtureof 54 g of styrene, 72 g of methyl methacrylate, 36 g of acrylonitrileand 18 g of glycidyl methacrylate was added continuously over 3 hoursand graft-polymerized. After this addition, the mixture was stirred foradditional 2 hours to terminate the reaction, to give the latex ofrubber-like polymer particles (B). The polymerization conversion ratiowas 99.5%. The resulting latex was used as it was.

Example 1 Production of a Modified Epoxy Composition

500 g of methyl ethyl ketone (hereinafter referred to as MEK; watersolubility at 25° C., 11% by weight) was introduced as an organic medium(C) component into a 3-L glass vessel kept at 25° C., and 420 g of theaqueous latex of rubber-like polymer particles (B) obtained inproduction Example 1 was added thereto and stirred. 450 g of methylisobutyl ketone (hereinafter referred to as MIBK; water solubility at25° C., 2% by weight) was added as an organic medium (D) to theresulting mixture (E) of the rubber-like polymer particles (B) and theorganic medium (C) under stirring. Separation of water from the mixedorganic medium layer was observed. After addition of MIBK, 210 g ofwater was added thereto and stirred. After stirring was terminated, themixture was left for 30 minutes, the aqueous layer was discharged, andthe dispersion (F) was recovered. The discharged aqueous layer was 460g. In the separated aqueous layer, the rubber-like polymer particles (B)were not recognized.

Then, the resulting dispersion (F) was mixed with 340 g of epoxy resin(A) (Epicote 828 (™, manufactured by Japan Epoxy resin Co., Ltd.)), andthen volatile components were distilled away at 80° C. for 4 hours underreduced pressure, to give an epoxy resin composition having therubber-like polymer particles (B) dispersed in the epoxy resin (A). Inthis mixing of the dispersion (F) with the epoxy resin (A), shakingmixing was used and strong mechanical stirring (stirring under highshear) was not required.

The dispersed state of the rubber-like polymer particles (B) in a curedproduct obtained from the epoxy resin composition was observed, and as aresult, the rubber-like polymer particles (B) were uniformly dispersedwithout agglomeration. The epoxy value (EEW) was 245 g/eq.

Comparative Example 1-1

500 g of methyl ethyl ketone (MEK) was introduced as an organic medium(C) into a 3-L glass vessel kept at 25° C., and 420 g of the aqueouslatex of rubber-like polymer particles (B) obtained in productionExample 1 was added thereto and stirred. 450 g of MEK was added again tothe resulting mixture (E) under stirring. After addition of MEK, 210 gof water was added thereto and stirred. Stirring was terminated and themixture was left for 30 minutes. Unlike Example 1, it was observed thatan aqueous layer was hardly formed, and the organic medium layer hadbeen emulsified to indicate that a large amount of water was contained.It was revealed that the efficiency of water separation was worse thanin the corresponding Example 1.

The same procedure as in Example 1 was carried out in attempting toobtain an epoxy resin composition having the rubber-like polymerparticles (B) mixed in the epoxy resin (A), but a large amount of waterremained in the epoxy resin, and the desired epoxy resin composition asshown in Example 1 could not be obtained.

Comparative Example 1-2

500 g of methyl ethyl ketone (MEK) was introduced as an organic medium(C) into a 3-L glass vessel kept at 25° C., and 420 g of the aqueouslatex of rubber-like polymer particles (B) obtained in productionExample 1 was added thereto and stirred. 210 g of water was added to theresulting mixture (E) under stirring. Stirring was terminated and themixture was left for 30 minutes. It was observed that an aqueous layerwas hardly formed, and the organic medium layer had been emulsified toindicate that a large amount of water was contained. It was revealedthat the efficiency of water separation was worse than in thecorresponding Example 1.

Comparative Example 1-3

500 g of methyl ethyl ketone (MEK) was introduced as an organic medium(C) into a 3-L glass vessel kept at 25° C., and 420 g of the aqueouslatex of rubber-like polymer particles (B) obtained in productionExample 1 was added thereto and stirred. Stirring was terminated and themixture (E) was left for 12 hours. The mixture (E) had been emulsified,the progress of water separation was hardly observed, and an aqueouslayer was not formed.

TABLE 1 Comparative Comparative Comparative Example 1 Example 1-1Example 1-2 Example 1-3 Organic solvent (C) MEK MEK MEK MEK Solubilityof water in 11% 11% 11% 11% organic solvent (C) Amount of introduced (C)500 g 500 g 500 g 500 g Amount of introduced (B) 420 g 420 g 420 g 420 gAmount of added water — — — — Organic solvent (D) MIBK MEK — —Solubility of water in  2% 11% — — organic solvent (D) Amount of added(D) 450 g 450 g — — Number of times dispersion 1 1 1 none (F) was washedwith water <210 g> <210 g> <210 g> <amount of added water> Waterseparability after left good not good not good not good Content ofrubber-like not detected — — — polymer particles (B) in aqueous layerDispersed state of good — — — rubber-like polymer particles (B) in acured product of epoxy resin composition

Example 2

252 g of aqueous latex of rubber-like polymer particles (B) was mixed ina mixed solvent of 306 g of methyl ethyl ketone (MEK) and 34 g of methylisobutyl ketone (MIBK) (solubility of water in the mixed solvent at 25°C., 10% by weight) as an organic medium (C) under stirring with astirring blade with a 3-tiered paddle wing in a 1 L mixing vessel keptat 25° C., 126 g of water was added thereto and stirred. While theresulting mixture (E) was stirred, 340 g of MIBK was added thereto asorganic medium (D). Stirring was terminated, then the mixture was leftfor 30 minutes, the aqueous layer was discharged, and the dispersion (F)was recovered. In the discharged aqueous layer, the rubber-like polymerparticles (B) were not recognized, and the rubber-like polymer particles(B) could be completely extracted in the organic medium layer.

In the same manner as in Example 1, the resulting dispersion (F) wasmixed with 204 g of epoxy resin (Epicote 828), and then volatilecomponents were distilled away under reduced pressure, whereby an epoxyresin composition was obtained.

The dispersed state of the rubber-like polymer particles (B) in a curedproduct obtained from the epoxy resin composition was observed, and as aresult, the rubber-like polymer particles (B) were uniformly dispersedwithout agglomeration. The amount of the emulsifier remaining in thedispersion (F) was 49% by weight based on the amount of the emulsifieradded at the time of production of the rubber-like polymer particle (B)latex.

Comparative Example 2-1

340 g of methyl isobutyl ketone (solubility of water at 25° C., 2.0% byweight) was introduced as an organic medium into a 1 L mixing vesselkept at 25° C., and 252 g of the aqueous latex of rubber-like polymerparticles (B) obtained in Production Example 1 was mixed therein understirring with a stirring blade with a 3-tiered paddle wing. 126 g ofwater was added thereto and stirred. After stirring was terminated, theseparation of the MIBK layer from the aqueous layer could be confirmed,but the rubber-like polymer particles (B) were not present in the MIBKlayer, and the rubber-like polymer particles (B) could not be extractedin the MIBK layer.

Comparative Example 2-2

340 g of acetone (water-soluble solvent dissolved mutually in water inan arbitrary ratio, that is, having a water solubility of ∞ at 25° C.)was introduced into a 1 L mixing vessel kept at 25° C., and 252 g of theaqueous latex of rubber-like polymer particles (B) obtained inproduction Example 1 was mixed therein under stirring with a stirringblade with a 3-tiered paddle wing. The rubber-like polymer particles (B)were agglomerated to generate a large number of large agglomeratedmaterials to make stirring difficult.

Example 3

A mixed solvent of 288 g of methyl ethyl ketone and 52 g of methylisobutyl ketone (solubility of water in the mixed solvent at 25° C.,9.2% by weight) was introduced as the organic medium (C) into a 1 Lmixing vessel kept at 25° C., and 252 g of the aqueous latex ofrubber-like polymer particles (B) obtained in Production Example 1 wasmixed therein under stirring with a stirring blade with a 3-tieredpaddle wing. 126 g of water was added thereto and stirred. 340 g of MIBKwas added as the organic medium (D) into the resulting mixture (E) understirring. After stirring was terminated, the mixture was left for 30minutes, the aqueous layer was discharged, and the dispersion (F) wasobtained. The content of the rubber-like polymer particles (B) in theaqueous layer was 1.2% by weight.

TABLE 2 Comparative Comparative Example 2 Example 2-1 Example 2-2Example 3 Organic solvent (C)  MEK (90) MIBK acetone  MEK (84.7) MIBK(10) MIBK (15.3) Solubility of water in 10% 2.0% ∞ 9.2% organic solvent(C) Amount of introduced (C) 340 g 340 g 340 g 500 g Amount ofintroduced (B) 252 g 252 g 252 g 420 g Amount of added water 126 g 126 g— 126 g Organic solvent (D) MIBK — — MIBK Solubility of water in  2% — 2% organic solvent (D) Amount of added (D) 340 g — — 340 g Number oftimes dispersion none none none none (F) was washed with water <amountof added water> Water separability after left good good not good goodinfeasible stirring due to flocculation of (B) Content of rubber-likenot detected 100% — 1.2% polymer particles (B) in by weight by weightaqueous layer Amount of the remaining 49% — — — emulsifier in dispersion(F) Dispersed state of good — — — rubber-like polymer particles (B) in acured product of epoxy resin composition

Example 4

365 g of methyl ethyl ketone (MEK) (solubility of water at 25° C., 11%by weight) was introduced as the organic medium (C) into a 1 L glassvessel at room temperature, and 252 g of the aqueous latex ofrubber-like polymer particles (B) obtained in production Example 1 wasmixed therewith under stirring. 400 g of methyl isobutyl ketone (MIBK)was added as the organic medium (D) to the resulting mixture (E) understirring. 252 g of water was added thereto and stirred. After stirringwas terminated, the mixture was left for 30 minutes, the aqueous layerwas discharged, and the dispersion (F) was obtained. In the dischargedaqueous layer, the rubber-like polymer particles (B) were not contained.Again, 400 g of water was added to and mixed with the dispersion (F).After the mixture was left for 60 minutes, the aqueous layer wasdischarged and the dispersion (F) was obtained. In the dischargedaqueous layer, the rubber-like polymer particles (B) were not containedeither.

In the same manner as in Example 1, the resulting dispersion (F) wasmixed with 204 g of epoxy resin (Epicote 828), and then volatilecomponents were distilled away under reduced pressure, whereby an epoxyresin composition was obtained.

The dispersed state of the rubber-like polymer particles (B) in a curedproduct obtained from the epoxy resin composition was observed, and as aresult, the rubber-like polymer particles (B) were uniformly dispersedwithout agglomeration. The amount of the emulsifier remaining in thedispersion (F) was 26% by weight based on the amount of the emulsifieradded to the latex.

Example 5

340 g of methyl ethyl ketone (MEK) was introduced into a 1 L mixingcontainer kept at 25° C., and 252 g of the aqueous latex of rubber-likepolymer particles (B) obtained in production Example 1 was mixedtherewith under stirring with a stirring blade with a 3-tiered paddlewing, and then stirring was terminated. 126 g of water was added theretoand stirred. 400 g of methyl isobutyl ketone was added as the organicmedium (D) to the resulting mixture (E) under stirring. After stirringwas terminated, the mixture was left for 30 minutes, the aqueous layerwas discharged, and the dispersion (F) was obtained. In the dischargedaqueous layer, the rubber-like polymer particles (B) were not contained.Again, 400 g of water was added to and mixed with the dispersion (F).After the mixture was left for 60 minutes, the aqueous layer wasdischarged and separated from the dispersion (F). In the dischargedaqueous layer, the rubber-like polymer particles (B) were not containedeither.

In the same manner as in Example 1, the resulting dispersion (F) wasmixed with 204 g of epoxy resin (Epicote 828), and then volatilecomponents were distilled away under reduced pressure, whereby an epoxyresin composition was obtained.

The dispersed state of the rubber-like polymer particles (B) in a curedproduct obtained from the epoxy resin composition was observed, and as aresult, the rubber-like polymer particles (B) were uniformly dispersedwithout agglomeration. The amount of the emulsifier remaining in thedispersion (F) was 32% by weight based on the amount of the emulsifieradded at the time of production of the rubber-like polymer particle (B)latex.

Example 6

340 g of methyl ethyl ketone (MEK) was introduced as the organic medium(C) into a 1 L mixing vessel kept at 25° C., and 252 g of the aqueouslatex of rubber-like polymer particles (B) obtained in productionExample 1 was mixed therewith under stirring with a stirring blade witha 3-tiered paddle wing, and then stirring was terminated. 126 g of waterwas added thereto and stirred. 400 g of methyl isobutyl ketone was addedas the organic medium (D) to the resulting mixture (E) under stirring.The mixture was left for 30 minutes, and the aqueous layer wasdischarged and separated from the dispersion (F). In the dischargedaqueous layer, the rubber-like polymer particles (B) were not contained.Again, 250 g of water was added to and mixed with the dispersion (F) andleft for 30 minutes, and then the aqueous layer was discharged andseparated from the dispersion (F). In the discharged aqueous layer, therubber-like polymer particles (B) were not contained either. Further,250 g of water was added thereto and stirred, the mixture was left for30 minutes without stirring, and the aqueous layer was discharged andthe dispersion (F) was obtained. In the discharged aqueous layer, therubber-like polymer particles (B) were not contained either.

In the same manner as in Example 1, the resulting dispersion (F) wasmixed with 204 g of epoxy resin (Epicote 828), and then volatilecomponents were distilled away under reduced pressure, whereby an epoxyresin composition was obtained.

The dispersed state of the rubber-like polymer particles (B) in a curedproduct obtained from the epoxy resin composition was observed, and as aresult, the rubber-like polymer particles (B) were uniformly dispersedas primary particles without agglomeration. The amount of the emulsifierremaining in the dispersion (F) was 10% by weight based on the amount ofthe emulsifier added at the time of production of the rubber-likepolymer particle (B) latex. The epoxy value (EEW) was 248 g/eq.

Example 7

340 g of methyl ethyl ketone (MEN) was introduced into a 1 L mixingcontainer kept at 25° C., and 252 g of the aqueous latex of rubber-likepolymer particles (B) obtained in production Example 1 was mixedtherewith under stirring with a stirring blade with a 3-tiered paddlewing, and then stirring was terminated. 126 g of water was added theretoand stirred. 400 g of ethyl acetate (solubility of water at 25° C., 3.4%by weight) was added as the component (D) to the resulting organic layer(E) under stirring. After the mixture was left for 30 minutes, theaqueous layer was discharged and separated from the dispersion (F). Inthe discharged aqueous layer, the rubber-like polymer particles (B) werenot contained. The dispersion (F) was left for 30 minutes, and then theaqueous layer was discharged and separated from the dispersion (F). Inthe discharged aqueous layer, the rubber-like polymer particles (B) werenot contained either.

In the same manner as in Example 1, the resulting dispersion (F) wasmixed with 204 g of epoxy resin (Epicote 828), and then volatilecomponents were distilled away under reduced pressure, whereby an epoxyresin composition was obtained.

The dispersed state of the rubber-like polymer particles (B) in a curedproduct obtained from the epoxy resin composition was observed, and as aresult, the rubber-like polymer particles (B) were uniformly dispersedas primary particles without agglomeration. The amount of the emulsifierremaining in the dispersion (F) was 32% by weight based on the amount ofthe emulsifier added at the time of production of the rubber-likepolymer particle (B) latex.

TABLE 3 Example 4 Example 5 Example 6 Example 7 Organic solvent (C) MEKMEK MEK MEK Solubility of water in 11% 11% 11% 11% organic solvent (C)Amount of introduced (C) 340 g 340 g 340 g 340 g Amount of introduced(B) 252 g 252 g 252 g 252 g Amount of added water — 126 g 126 g 126 gOrganic solvent (D) MIBK MIBK MIBK ethyl acetate Solubility of water in 2%  2%  2% 3.4%  organic solvent (D) Number of times dispersion 2 1 2 1(F) was washed with water <252 g/  <252 g> <252 g/  <252 g> <amount ofadded water)  400 g>  252 g> Separability of (F) from the good good goodgood aqueous layer after left Content of rubber-like not detected notdetected not detected not detected polymer particles (B) in aqueouslayer Amount of the remaining 26% 32% 10% 32% emulsifier in dispersion(F) Dispersed state of good good good good rubber-like polymer particles(B) in a cured product of epoxy resin composition

INDUSTRIAL APPLICABILITY

By using the production process of the present invention, arubber-modified epoxy resin composition excellent in the dispersed stateof rubber-like polymer particles (B) and superior in qualities with lesscontaminant can be produced easily and efficiently.

1. A process for producing a curable epoxy resin composition comprisingpolymer particles (B) and a curable epoxy resin (A), the polymerparticles (B) comprising 5 to 50% by weight of a shell layer (B-2) and50 to 95% by weight of a rubber particle core (B-1), and the polymerparticles (B) being in an independently dispersed state of substantiallyprimary particles in the epoxy resin (A); the process comprising thesteps of bringing an organic medium (C) showing partial solubility inwater into contact with an aqueous latex of polymer particles (B), thenbringing an organic medium (D) having lower partial solubility in waterthan that of (C) into contact therewith to separate an aqueous layersubstantially from the polymer particles (B), discharging the aqueouslayer to obtain a dispersion (F) consisting essentially of the polymerparticles (B) and the mixed organic mediums (C) and (D), withoutisolating the polymer particles (B) as a coagulated material, dissolvinga curable epoxy resin (A) in the dispersion (F), and removing volatilecomponents; and the polymer particles (B) being in an independentlydispersed state of substantially primary particles in the dispersion(F).
 2. The process for producing a curable epoxy resin compositionaccording to claim 1, wherein after the organic medium (C) showingpartial solubility in water is brought into contact with the aqueouslatex of polymer particles (B) and then the organic medium (D) havinglower partial solubility in water than that of (C) is brought intocontact therewith to separate an aqueous layer substantially from thepolymer particles (B), and before the dispersion (F) is mixed with thecurable epoxy resin (A), the dispersion (F) is washed by bringing it atleast once into contact with water.
 3. The process for producing acurable epoxy resin composition according to claim 1, wherein thepartial solubility of the organic medium (C) in water is defined asfollows: a solubility of water in the organic medium (C) at 25° C. is 9to 40% by weight.
 4. The process for producing a curable epoxy resincomposition according to claim 1, wherein the organic mediums (C) and(D) are a combination not forming two-component azeotropic mixture. 5.The process for producing a curable epoxy resin composition according toclaim 1, wherein the polymer particles (B) are obtained bygraft-polymerizing 5 to 50% by weight of the shell layer (B-2)comprising at least one monomer selected from the group consisting of(meth)acrylates, aromatic vinyls, vinyl cyanides, unsaturated acidderivatives, (meth)acrylamide derivatives and maleimide derivatives,with 50 to 95% by weight of the rubber particle core (B-1) comprising arubber elastic body composed of not less than 50% by weight of at leastone monomer selected from the group consisting of diene monomers and(meth)acrylate monomers and less than 50% by weight of anothercopolymerizable vinyl monomer, or a polysiloxane rubber elastic body, ora mixture thereof.
 6. The process for producing a curable epoxy resincomposition according to claim 5, wherein the shell layer (B-2) in thepolymer particle (B) comprises a monomer having reactivity with an epoxyresin or a curing agent.
 7. A curable epoxy resin composition obtainedby the process described in claim
 1. 8. A cured molded productcomprising the curable epoxy resin composition of claim 7 cured with acuring agent.
 9. A dispersion (F) consisting essentially of polymerparticles (B) and mixed organic mediums (C) and (D), the polymerparticles (B) comprising 5 to 50% by weight of a shell layer (B-2) and50 to 95% by weight of a rubber particle core (B-1), and the polymerparticles (B) being in an independently dispersed state of substantiallyprimary particles in the dispersion (F); wherein the dispersion (F) isobtained by bringing an organic medium (C) showing partial solubility inwater into contact with an aqueous latex of polymer particles (B),bringing an organic medium (D) having lower partial solubility in waterthan that of (C) into contact therewith to separate an aqueous layersubstantially from the polymer particles (B), and discharging theaqueous layer to obtain the dispersion (F) without isolating the polymerparticles (B) as a coagulated material.